Morphological evolution in single-crystalline Bi2Te3 nanoparticles, nanosheets and nanotubes with different synthesis temperatures

A general surfactant-assisted wet chemical route has been developed for the synthesis of a variety of bismuth telluride (Bi₂Te₃) single-crystalline nanostructures with varied morphologies at different temperatures in which hydrazine hydrate plays as an important solvent. Bi₂Te₃ sheet grown nanoparticles, nanosheets and nanotubes have been synthesized by a simplest wet chemical route at 50, 70 and 100 °C within 4 h. Bi₂Te₃ sheet grown nanoparticles are obtained in agglomerate state and they are found with many wrinkles. Various types of Bi₂Te₃ nanotubes are also found which are tapered with one end open and the other closed. X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) pattern and energy dispersive X-ray (EDX) spectroscopy were employed to characterize the powder product. It is found that all nanoparticles, nanosheets and nanotubes are well-crystallized nanocrystals and morphologies of the powder products are greatly affected by different synthesis temperatures. The formation mechanisms of bismuth telluride nanostructures are also discussed.     

Hydrothermal synthesis and thermoelectric properties of nanostructured Bi0.5Sb1.5Te3 compounds

Single-phase Bi_0.5Sb_1.5Te₃ compounds have been prepared by hydrothermal synthesis at 150 °C for 24 h using SbCl₃, BiCl₃ and tellurium powder as precursors. X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) have been applied to analyze the phase distributions, microstructures and grain sizes of the as-grown Bi_0.5Sb_1.5Te₃ products. It is found that the hydrothermally synthesized Bi_0.5Sb_1.5Te₃ nanopowders have a morphology dominated by irregular hexagonal sheets due to the anisotropic growth of the crystals. The Bi_0.5Sb_1.5Te₃ nanosheets are parallelly stacked in certain direction to form sheet-agglomerates attribute to the temperature gradients in the solution.     

Facile synthesis and thermoelectric studies of n-type bismuth telluride nanorods with cathodic stripping Te electrode

Bismuth telluride (Bi₂Te₃) nanorods (NRs) of n-type thermoelectric materials were prepared using an electrogenerated precursor of tellurium electrode in the presence of Bi³⁺ and mercapto protecting agent in aqueous solution under atmosphere condition. The optimal preparation conditions were obtained with ratio of Bi³⁺ to mercapto group and Te coulomb by photoluminescence spectra. The mechanism for generation of Bi₂Te₃ precursor was investigated via the cyclic voltammetry. The highly crystalline rhombohedral structure of as-prepared Bi₂Te₃ NRs with the shell of Bi₂S₃ was evaluated with high resolution transmission electron microscopy (HRTEM) and powder X-ray diffraction (XRD) spectroscopy. The near-infrared absorption of synthetic Bi₂Te₃ NRs was characterized with spectrophotometer to obtain information of electron at interband transition. The thermoelectric performance of Bi₂Te₃ NRs was assessed with the result of electrical resistivity, Seebeck coefficient, thermal conductivity, and the figure of merit ZT parameters, indicating that thermoelectric performance of as-prepared Bi₂Te₃ nanocrystals was improved by reducing thermal conductivity while maintaining the power factor.     

Bi2Te3纳米结构的制备、磁性掺杂和结构表征

通过液相法制备Bi2Te3纳米管,设计并优化了Co离子的掺磁方案。通过扫描电镜、透射电镜、X射线衍射、红外光谱和能量色散X射线光谱对制备的样品进行了结构表征。实验结果表明,液相法可制备出晶相良好的Bi2Te3纳米管、Co离子均匀掺杂的Bi2Te3纳米结构样品。     

Influence of sintering temperature on thermoelectric properties of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>/Polythiophene composite materials

Bi₂Te₃/Polythiophene (PTH) thermoelectric bulk composite materials were prepared by a two-step method. Firstly, Bi₂Te₃ and PTH nanopowders were prepared by hydrothermal synthesis and chemical oxidative polymerization, respectively. Secondly, the mixture of the Bi₂Te₃ and PTH nanopowders (50:50 wt) was pressed under vacuum at 80 MPa and 298, 473, or 623 K. For comparison, Bi₂Te₃ powders were hot pressed at 623 K. The bulk materials were analyzed by conventional methods, such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA) and field emission scanning electron microscopy equipped with electron dispersive X-ray spectroscopy. The XRD and TGA results showed that the PTH decomposed when the hot pressing temperature exceeded 473 K, and Bi₂Te₂S phase was formed. The thermoelectric properties of the bulk composite materials were investigated. The composite pressed at 623 K showed a higher power factor, ~2.54 μ Wm⁻¹ K⁻² at 473 K, which is as ~20 times as that of the composite pressed at 473 K, although, it is still much lower than that of the pressed Bi₂Te₃ material (~1,266 μ Wm⁻¹ K⁻² at 348 K).     

Preparation of the Bi8Sb32Te60 solid solution by mechanical alloying

Bi₂Te₃, Sb₂Te₃ and Bi₈Sb₃₂Te₆₀ thermoelectric materials have been prepared by mechanical alloying using a high energy planetary ball mill. The alloy formation was followed by X-ray diffraction (XRD), the morphology by scanning electron microscopy (SEM) and the composition by electron microprobe. The samples of Bi₈Sb₃₂Te₆₀ were prepared in a reasonable milling time (less than 8 h) by mechanical alloying of binary alloys (Bi₂Te₃ and Sb₂Te₃). The single phase Bi₈Sb₃₂Te₆₀ solid solution obtained presents convenient stoichiometry and good homogeneity in composition. This revised version was published online in November 2006 with corrections to the Cover Date.     

Bi2S3-modified TiO2 nanotube arrays: easy fabrication of heterostructure and effective enhancement of photoelectrochemical property

A novel heterostructure of Bi₂S₃ nanoparticles (NPs) and TiO₂ nanotube arrays (NAs) was fabricated by a conventional hydrothermal method. The morphological features and the X-ray diffractogram of the obtained Bi₂S₃/TiO₂ NAs were characterized by field-emission scanning electron microscopy, transmission electron microscopy, and powder X-ray diffraction. The photoelectrochemical property of Bi₂S₃/TiO₂ NAs was also evaluated. The results demonstrated that photoelectrochemical solar cells based on Bi₂S₃/TiO₂ NAs had a short-circuit current of 4.54 mA/cm² and photoelectric conversion efficiency of 1.86 %. Surface photovoltage spectroscopy and field-induced surface photovoltage spectroscopy data indicated the existence of a strong interfacial electronic field between the two components Bi₂S₃ NPs and TiO₂ NAs, which can enhance the separation of photogenerated charge carriers.     

Structure and microstructure of In4Te3 nanopowders prepared by solid state reaction

In this paper, we investigated the structure and microstructure of In₄Te₃ nanopowders obtained by mechanically alloying an In₇₅Te₂₅ powder mixture. Structural, chemical, thermal and vibrational studies of the In₇₅Te₂₅ powder mixture were carried out using X-ray diffraction, energy dispersive spectroscopy, transmission electron microscopy, differential scanning calorimetry and Raman spectroscopy. The orthorhombic In₄Te₃ phase (In₃Se₄-type) was nucleated in 2 h of synthesis, although non-reacted tetragonal indium (In) was still present at that time. Small amounts of cubic In₂O₃ phase were observed after 31 h of synthesis. Rietveld analyses allowed the measurement of mean crystallites sizes and phase fraction variations when milling times were increased. These analyses showed that, after 31 h of synthesis, about 65 wt% of In₄Te₃ phase contained mean crystallite sizes smaller than 27 nm and microstrains greater than 1.5%. The crystallite and interfacial components sizes were determined by high resolution transmission electron microscopy. Differential scanning calorimetry measurements showed the influence of nanometric crystallite sizes on the melting of the In₄Te₃ and non-reacted In phases. Raman measurements showed that the trigonal Te and α-TeO₂ modes, observed for the precursor Te powder, are absent for the sample milled for 31 h. The structural stability of the nanocrystalline phases of the In₇₅Te₂₅ sample milled for 31 h was attested by X-ray diffraction measurements performed twelve months after its production.     

Physical properties of Bi2 (Te,Se)3 and Bi2Se1.2Te1.8 prepared using solid-state microwave synthesis

Bi₂(Te, Se)₃ and Bi₂Se_1.2Te_1.8 bulk products were synthesised using standard solid-state microwave synthesis. The Bi₂(Te, Se)₃ and Bi₂Se_1.2Te_1.8 were then deposited thermally onto glass substrates at a pressure of 10^? 6 Torr. The structure of the samples was analysed using X-ray diffraction (XRD), and the powders and thin films were observed to be polycrystalline and rhombohedral in structure. The surface morphology of the samples was determined using scanning electron microscopy (SEM). From the measurements of optical properties, the energy gap values for the Bi₂Te₃, Bi₂Se₃, and Bi₂Se_1.2Te_1.8 thin films were 0.43, 0.73, and 0.65 eV, respectively.     

Fast preparation of Bi2GeO5 nanoflakes via a microwave-hydrothermal process and enhanced photocatalytic activity after loading with Ag nanoparticles

In this work, a facile and rapid microwave-assisted hydrothermal route has been developed to prepare Bi₂GeO₅ nanoflakes. Ag nanoparticles were subsequently deposited on the Bi₂GeO₅ nanoflakes by a photoreduction procedure. The phases and morphologies of the products were characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectrum (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and UV–vis diffuse reflectance spectroscopy. Photocatalytic experiments indicate that such Ag/Bi₂GeO₅ nanocomposite possesses higher photocatalytic activity for RhB degradation under UV light irradiation in comparison to pure Bi₂GeO₅. The amount of Ag in the nanocomposite affects the catalytic activity, and 3 wt% Ag showed the highest photodegradation efficiency. Moreover, the catalyst remains active after four consecutive tests. The present study provides a new strategy to design composite materials with enhanced photocatalytic activity.     

Fabrication of three-dimensional snowflake-like bismuth sulfide nanostructures by simple refluxing

Three-dimensional snowflake-like bismuth sulfide nanostructures were successfully synthesized by simple refluxing at 160 °C in ethylene glycol, using bismuth citrate and thiourea as reactants. The crystal structures and morphologies of the products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDX). The Bi₂S₃ nanostructure was built up by highly ordered one-dimensional Bi₂S₃ nanorods, which was aligned in an orderly fashion. Ethylene glycol plays a critical role in the creation of bismuth sulfide three-dimensional nanostructures, which serves as an excellent solvent and structure director. Bismuth citrate, a linear polymer, also makes for the formation of the three-dimensional nanostructures.     

Synthesis and characterization of an electro-deposited polyaniline-bismuth telluride nanocomposite — A novel thermoelectric material

The present work consists of synthesis and characterization of a novel thermoelectric material polyaniline (PANI)-bismuth telluride (Bi₂Te₃) nanocomposite using simultaneous electrochemical reactions and deposition method. The inorganic bismuth nitrate has been used as a dopant for polyaniline to achieve high electrical conductivity. A semi-batch mode of operation has been employed to control the rate of deposition of an individual component and thus the molecular architecture of the composite. The electro-deposited composite film on ITO coated glass substrate has been characterized by X-ray diffraction analysis (XRD), FTIR analysis, scanning electron microscope (SEM), and transmission electron microscope (TEM). The microscopic analysis reveals the formation of rod-like nanostructures of diameter less than 100 nm. It has been found that smaller molecules of Bi₂Te₃ are dispersed in the macromolecules of PANI. The nanocomposite has been characterized by thermoelectric power.     

Synthesis of single crystal Bi2Te3 nanoplates via an inorganic-surfactant-assisted solvothermal route

Single crystal Bi₂Te₃ nanoplates have been successfully obtained by a solvothermal method adopting a lamellar structure as the precursor. Various techniques such as X-ray diffraction (XRD), field-emission scanning electron microscope (FESEM), high-resolution transmission electron microscope (HRTEM), and selected area electron diffraction (SAED) have been used to characterize the obtained products. The results show that the as-synthesized samples are rhombohedral-structured Bi₂Te₃ single-crystal nanoplates, whose growth direction is perpendicular to c-axis. In addition, some important experiment parameters such as the water/ethanol volume ratio and pH value have been discussed.     

Sonochemical synthesis, characterization, and photocatalytic properties of Bi2−x Sb x WO6 nanorods

We report an efficient route for the sonochemical synthesis of Bi_2?x Sb _x WO₆ (x = 0, 0.01, 0.02, 0.05, 0.1, and 2) nanorods using bismuth nitrate/antimony chloride and sodium tungstate as precursors. The products obtained have been characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and UV–Vis diffuse reflectance spectroscopy. The photoactivities of all the samples for the Rhodamine-B (RhB) photodegradation were investigated systematically under UV and visible light irradiation. The results of the photocatalytic degradation of RhB in aqueous solution showed that 2–5 % antimony ion doping greatly improved the photocatalytic efficiency of sonochemically synthesized Bi₂WO₆ nanorods under both UV and visible radiation compared to its undoped counterpart. Among all the samples, the Sb₂WO₆ nanorods exhibited the highest photodegradation efficiency since 86 % of RhB could be photodegraded in 90 min under UV radiation. The stability of the photocatalysts was ascertained using FT-IR and Raman spectroscopy.     

Cu2S nanostructures prepared by Cu-cysteine precursor templated route

A facile Cu-cysteine precursor templated route for the synthesis of Cu₂S nanowires, dendritic-like and flowerlike nanostructures is reported. The Cu-cysteine precursors are prepared through the reaction between Cu²⁺, l-cysteine and ethanolamine at room temperature, and the morphologies of Cu-cysteine precursors can be controlled by adjusting the molar ratio of l-cysteine to Cu²⁺. The Cu-cysteine precursors are used as both templates and source materials for the subsequent preparation of polycrystalline Cu₂S nanostructures by thermal treatment, and the morphologies of the precursors can be well preserved after the thermal transformation to Cu₂S nanostructures. The samples are characterized using X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy and Fourier transform infrared spectroscopy.     

Rapid synthesis of Bi2S3 nanocrystals with different morphologies by microwave heating

Single-crystalline Bi₂S₃ nanocrystals with urchinlike and rod-like morphologies have been successfully synthesized using Bi₂O₃, HCl, Na₂S₂O₃ and ethylene glycol (EG) by a simple and fast microwave heating method. Both urchinlike and rod-like Bi₂S₃ nanostructures could be formed under microwave heating at 190 °C for 30 s. Urchin-like Bi₂S₃ nanostructures were prepared using sodium dodecyl sulfate (SDS) or in the absence of any surfactant. However, Bi₂S₃ nanorods were obtained in the presence of cetyltrimethylammonium bromide (CTAB). The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), electron diffraction (ED) and ultraviolet-visible (UV-Vis) absorption spectra.     

Structural, electrical and optical properties of Bi2Se3 and Bi2Se(3−x)Tex thin films

Thin films of Bi₂Se₃, Bi₂Se_2.9Te_0.1, Bi₂Se_2.7Te_0.3 and Bi₂Se_2.6Te_0.4 are prepared by compound evaporation. Micro structural, optical and electrical measurements are carried out on these films. X-ray diffraction pattern indicates that the as-prepared films are polycrystalline in nature with exact matching of standard pattern. The composition and morphology are determined using energy dispersive X-ray analysis and scanning electron microscopy (SEM). The optical band gap, which is direct allowed, is 0.67 eV for Bi₂Se₃ thin films and the activation energy is 53 meV. Tellurium doped thin films also show strong optical absorption corresponding to a band gap of 0.70-0.78 eV. Absolute value of electrical conductivity in the case of tellurium doped thin film shows a decreasing trend with respect to parent structure.     

Phosphorus-doped bismuth telluride films by electrodeposition

Phosphorus-doped Bi₂Te₃ films were synthesized on a stainless-steel electrode by electrochemical deposition. X-ray diffraction, scanning electron microscopy and transmission electron microscopy confirmed that the films are single-phased Bi₂Te₃ solid solutions with a rhombohedral structure. The as-prepared films exhibit n-type characteristics with the Hall coefficient −1.76E−2 m³ C⁻¹ and the electrical conductivity 280 S cm⁻¹. The thermal conductivity is 0.47 W m⁻¹ K⁻¹, which is as low as one-third of the value observed in the bulk material. The doped P atoms occupy the interstitial positions between the two adjacent Te(1) layers connected by Van der Waals interaction in Bi₂Te₃.     

Mechanochemical synthesis and characterization of Ni<Subscript>25</Subscript>Te<Subscript>75</Subscript> nanocrystalline alloy

Ni₂₅Te₇₅ nanocrystalline alloy containing trigonal NiTe₂ and Te nanocrystals was prepared through mechanochemical processing of pure elemental tellurium and nickel powders in argon atmosphere. The Ni₂₅Te₇₅ samples processed from 3 h to 30 h milling times were characterized by X-ray powder diffraction, transmission electron microscopy, magnetization and Raman spectroscopy. Trigonal NiTe₂ crystals with average size of 16 nm can be obtained after only 3 h of processing time. For longer milling times, the trigonal NiTe₂ phase becomes majority (about 70% with 30% for nanometric Te and no pure Ni was detected) and its average crystallite size slightly increases to 20 nm. Transmission electron microscopy images and electron diffraction patterns confirm the nanometric size of the crystalline domains in the agglomerated particles. The magnetic properties of the Ni₂₅Te₇₅ powders are dependent on synthesis time, suggesting a paramagnetic behavior mainly associated with the NiTe₂ nanophase. Raman spectra showed peaks that can be associated with unreacted Te and tellurium oxides modes, but it also showed several modes that can be attributed to trigonal NiTe₂ nanophase. The high-pressure experiments showed no phase transitions for NiTe₂ up to 17 GPa and Te phase transitions from form I to forms II and III occurred simultaneously at 4.5 GPa, remaining up to 12 GPa; after that, only reflections of Te-III and the NiTe₂ were observed. All the phase transitions observed with pressure are reversible after decompression. The bulk modulus determined from the least-squares fit of first-order Murnaghan equation of states is 110 GPa for the NiTe₂ nanophase and 28 GPa for Te-I.     

Bi2S3 nanotubes: Facile synthesis and growth mechanism

Synthesis of tubular nanomaterials has become a prolific area of investigation due to their wide range of applications. A facile solution-based method has been designed to fabricate uniform Bi₂S₃ nanotubes with average size of 20 nm × 160 nm using only bismuth nitrate (Bi(NO₃)₃·5H₂O) and sulfur powder (S) as the reactants and octadecylamine (ODA) as the solvent. Powder X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and energy dispersive spectroscopy (EDX) experiments were employed to characterize the resulting Bi₂S₃ nanotubes and the classic rolling mechanism was applied to explain their formation process.